r 


A STUDY  OF  THE  PRODUCTS  OBTAINED  BY  THE 
SOLVENT  ACTION  OF  DI-PHENYL  ETHER 
ON  FRANKLIN  COUNTY  COAL 


BY 

ARVID  HENRY  BERG 


THESIS 

FOR  THE 

DEGREE  OF  BACHELOR  OF  SCIENCE 


CHEMISTRY 


COLLEGE  OF  LIBERAL  ARTS  AND  SCIENCES 


UNIVERSITY  OF  ILLINOIS 


Digitized  by  the  Internet  Archive 

in  2015 


https://archive.org/details/studyofproductsoOOberg 


ACKNOWLEDGMENT 

This  work  war.  undertaken  in  the  Chemical  Laboratory 
of  the  University  of  Illinois.  The  problem  was  suggested 
by  Dr.  Layng  and  its  completion  was  due  largely  to  his 
timely  advice  and  helpful  suggestions.  I wish  to  take  this 
opportunity  of  expressing  my  appreciation  to  him. 


> 


« 

. 


TABLE  OF  CONTENTS. 


Page 

Acknowledgment  i 

I.  Introduction  1-  10 

1.  Nature  of  Problem  1 

2.  Historical  2-  10 

II.  Experimental  11  -13 

1.  Solvent  Methods  11  -12 

2.  Carbonization  Methods  12  -13 

III.  Results  14  -16 

IV.  Discussion  of  Results  17  -19 

V.  Conclusion  20 

VI.  Bibliography  21  -22 


A STUDY  OF  THE  PRODUCTS  OBTAINED  BY  THE  SOLVENT 
ACTION  OF  DI- PHENYL  ETHER  ON  FRANKLIN  COUNTY  COAL 

I.  INTRODUCTION 

1. -  Nature  of  the  problem. 

A Knowledge  of  the  constitution  of  coal, which  will  explain 
why  some  coals  coke  and  others  do  not,  has  been  sought  thru 
various  channels  of  research.  The  means  employed  in  this  search 
have  been  ultimate  analyses,  microscopic  studies,  fractional 
carbonizations,  and  solvents.  Each  onehas  given  us  some  infor- 
mation and  as  a result  various  theories  have  arisen  from  time  to 
time,  which  attempt  to  give  the  desired  explanation.  It  is  the 
intent  of  this  work  to  find,  if  possible,  some  differences  in 
fresh  and  oxidized  coals  thru  a study  of  the  products  obtained  by 
the  use  of  a solvent,  which  in  this  case  is  di- phenyl  ether,  to 
confirm  the  present  theories  or  prove  a new.  The  work  will  not  be 
confined  to  the  extracts  alone  but  to  the  coals  and  the  residues 
as  well. 

2. -  Historical. 

In  order  to  proceed  with  the  problem,  it  is  necessary  to  re- 
view some  of  the  work  that  has  been  done  by  former  investigators, 
which  has  led  to  our  present  theories. 

White  and  Thiessen^ , in  their  great  classic  went  deeply  into 
the  problem  of  the  origin  and  constitution  of  coal  and  thru  their 
studies  brought  out  authoritatively  the  idea  that  coal  consists 
of  two  different  constituents,  which  they  called  cellulosic  and 

O 

resinic.  Cross  and  Bevan  studied  the  action  of  sulphuric  acid  on 
cellulose  and  coal  and  they  came  to  the  conclusion  that  there 


(2) 

could  "be  two  possibilities  for  the  formation  of  coal.  The  first 
possibility  is  the  lignifying  of  substances  which  originally  con- 
sisted mainly  of  cellulose  and  the  second  is  the  combining  of  the 
cellulose  and  the  resinic  parts,  found  elsewhere  in  the  plant  and 
formed  perhaps  thru  the  oxidation  of  the  hydrocarbons. 

Anderson-^,  inf  a continuation  of  the  work  done  earlier  by 
himself  and  Roberts  on  the  treatment  of  coal  with  carbon  dioxide 
and  nitric  acid  at  31£$^C.,  came  to  the  conclusion  that  u whether 
or  not  different  coals  contain  bodies  that  are  in  a genetic  or 
homologous  series,  such  bodies  form  at  least  only  a part,  and  it 
may  be  but  a minor  part,  of  the  mineral.  Furthermore,  that  a con- 
siderable part  of  the  organic  matter  consists  of  a complex  com- 
pound comparatively  rich  in  nitrogen  and  that,  above  all,  resin- 
ous matter  is  present  to  a small  but  fairly  constant  degree'.' . 

4 

Parr  and  Francis  conclude  from  a study  of  the  literature 
as  follows:  (1)  That  coal  was  not  derived  from  cellulose  alone, 
but  from  a combination  of  cellulose  and  aromatic  bodies.  (2)  That 
the  main  portion  of  the  coal  is  a definite  unit,  associated  with 
a small  amount  of  bitumen  or  resinous  matter.  (3)  That  the  struct- 
ure and  the  properties  of  coal  are  greatly  modified  by  the  re- 
moval of  certain  portions  of  the  coal  by  one  means  or  another, 
mainl#  solvents. 

David  17hite5  explains  the  coking  qualities  of  coal  as  de- 
pendent on  the  presence  or  the  absence  of  certain  gelatinous  algae 
The  more  of  the  algae  present,  the  closer  the  percentage  of  hy- 
drogen and  oxygen  comes  to  that  of  bitumen,  that  is  higher  hydro- 
gen lower  oxygen  and  therefore  better  coking.  He  concludes  that 


. 


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1 

(3) 

coals  high  in  volatile  matter  and  showing  high  bituninization  will 
coke  and  the  degree  of  this  bituminization  will  be  indicated  by  the 
ratio  of  hydrogen  to  oxygen  in  the  dry  coal.  From  this  assumption 
or  apparent  fact  he  has  developed  the  theory  of  the  H:C  ratio  as 
being  an  indication  of  the  coking  power  of  the  coal. 

Wheeler  , working  in  conjunction  with  Burgess  and  Clark  on 
the  carbonization  method,  has  advanced  several  important  facts  in 
conjunction  with  the  carbonization  theory.  There  has  developed 
certain  contradictory  evidence  from  time  to  time,  which  will  be 
discussed  later.  Their  researches  brought  out  the  following:  (1) 
There  is  a well  defined  temperature  between  700°  and  800° C.  which 
coresponds  with  a marked  and  rapid  increase  in  the  quantity  of 
hydrogen  evolved.  (2)  Evolution  of  hydrocarbons  of  the  paraffin 
series  ceases  almost  entirely  at  temperatures  above  750°C.  (3) 
Ethane,  propane,  butane,  and  probably  higher  members  of  the  par- 
affin series  form  a large  percentage  of  the  gases  evolved  at  tem- 
peratures below  450  C.  (4)  The  rate  of  CO  evolution  is  uniform 
thruout  a distillation  at  any  one  temperature,  and  is  maintained 
up  to  the  end.  While  the  rates  of  evolution  of  the  other  gases 
fall  off,  the  CO  rate  increases  with  the  temperature.  From  these 
results  they  argue  that  coal  contains  two  types  of  compounds  of 
different  degrees  of  ease  of  decomposition.  The  one  , the  least 
stable,  yields  the  paraffin  hydrocarbons  and  no  hydrogen.  The 
other,  the  one  decomposing  with  greater  difficulty,  yields  hydro- 
gen alone  ( or  possibly  hydrogen  and  the  oxides  of  carbon) . They 
likewise  claim  that  probably  the  difference  between  one  coal  and 
another  is  determined  by  the  proportion  in  which  the  two  types  of 


(4) 

compounds  exist. 

Porter  and  Taylor?  working  with  what  they  considered  re- 
presentative coals  of  the  United  States  found  disagreements  with 
the  results  and  the  conclusions  of  Wheeler.  Their  results  can  he 
critized  from  the  fact  that  they  used  old  coals,  which  later  have 
been  shown  to  have  been  oxidized  and  therefore  altered,  and  also 
from  the  fact  that  their  analyses  of  the  gases  show  no  oxygen. 
Their  results  are  as  follows:  (1)  More  than  two  thirds  of  the  or- 
ganic substance  of  coal  is  decomposed  at  temperatures  below  500°C. 
(2)  The  first  decomposition  occuring  in  any  type  of  coal  as  the 
temperature  is  raised  is  the  breaking  down  of  certain  oxygen- 
containing  substances  related  to  cellulose,  the  products  being 
cheifly  COg,  GO,  and  water.  (3)  Coal  probably  breaks  down  more  or 
less  at  all  temperatures  but  the  temperatures  at  which  coal  com- 
mences to  give  off  volatile  matter  in  appreciable  quantities  is  at 
250cC.  or  lower.  (4)  paraffin  hydrocarbons  predominate  at  tem- 
peratures below  400°C.  (5)  Thermal  decomposition  of  the  volatile 
matter  occursvery  easily  at  temperatures  around  750°C.  (6)  Dis- 
tillation at  temperatures  above  750JC.  yields  gases  in  which  hy- 
drogen largely  predominates  whether  secondary  reactions  are  pre- 
vented or  not,  but  secondary  decomposition  of  the  volatile  matter 
will  increase  the  total  gas  yield  at  the  expense  of  the  tar.  (7) 
Water  of  decomposition  is  produced  above  250°C.  but  in  greater 
amount  below  530°C.  than  above.  This  water  vapor  may  react  with 
tar  vapors  or  gases  in  passing  out  of  the  retort  during  high  tem- 
perature carbonization. 

Porter  and  Taylor  take  issue  with  Wheeler  on  the  proposition 
that  the  appearance  or  rapid  increase  of  hydrogen  between  700  C. 


(5) 

and  800°G.  marks  a really  defined  decomposition  point  or  critical 
point  at  which,  after  the  decomposition  of  the  resinic  material, 
that  of  the  more  stable,  the  cellulosic,  commences.  Th  y think 
that  the  marked  increase  in  the  H,;;i  may  be  due  to  secondary  decom- 
position of  the  volatile  constituents  of  the  coal.  They  propose 
the  following  hypothesis  for  the  constitution  of  coal:  All  kinds 
of  coal  consist  of  cellulosic  degradation  products,  more  or  less 
altered  by  the  process  of  aging,  together  with  the  derivatives  of 
the  resinous  materials  in  different  proportions,  also  more  or  less 
altered.  These  substances  are  many  in  number  and  closely  graded 
into  one  another  in  their  nature  and  composition.  They  all  under- 
go decomposition  on  moderate  heating,  some , however , decompose 
more  rapidly  than  others  at  the  lower  temperatures.  The  less  al- 
tered cellulosic  derivatives  decompose  more  easily  than  the  more 
altered  derivatives  or  the  resinous  derivatives.  The  cellulosic 
derivatives  decompose  on  moderate  heating  so  as  to  yield  water, 
carbon  dioxide,  cenbon  monoxide,  and  hydrocarbons,  giving  less  of 
the  first  three  products  the  more  mature  and  altered  they  are. 

The  resinous  derivatives  on  the  other  hand  decompose  on  moderate 
heating  so  as  to  yield  principally  the  paraffin  hydrocarbons  with 
probably  hydrogen  as  a direct  decomposition  product.  The  more 
mature  bituminous  coals  with  good  coking  qualities  contain  a large 
percentage  of  resinous  material  and  their  cellulosic  material  has 
been  highly  altered.  The  younger  bituminous  coals  consist  chiefly 
of  cellulosic  material  much  less  altered  than  thatein  the  older 
coals.  They  undergo  a large  amount  of  decomposition  below  their 
fusion  point  and  for  that  reason  do  not  coke. 


* 

. 


: 


, 


(6) 


Lewes®  points  to  the  fact  that  if,  as  Burgess  end  Wheeler 
claim,  the  cellulosic  constituent  decomposes  last;  then,  since  it 
is  the  cellulosic  part  that  is  high  in  hydrogen  and  low  in  oxygen, 
an  analysis  of  the  coke  donned  at  450°C.  should  show  higher  oxy- 
gen and  lower  hydrogen  than  the  original  coal,  due  to  the  elim- 
ination of  the  resinic  material  which  is  supposedly  high  in  hy- 
drogen as  compared  to  oxygen.  He  tried  this  "but  discovered  that  , 
though;  the  coke  was  lower  in  hydrogen  than  the  coal,  it  was  also 

9 

loY/er  in  oxygen.  White  , in  his  studies  of  resins,  found  that  some 
resins  have  excess  oxygen  over  hydrogen. 

Lewes  view  of  the  mechanism  of  coking  is  as  follows:  Water 
evaporates  and  then  recondenses  in  that  part  of  the  coal,  which  is 
cool  enough.  Hygroscopic  water  comes  off  first  and  then  hunus 
bodies  commence  to  decompose  and  they  give  as  their  first  product 
water.  As  the  temperature  rises  to  3$>P°C . or  above,  the  coal  be- 
comes semi-fluid.  Decomposition  of  all  the  coal  bodies  commences 
and  increases  rapidly  in  vigor  wi th  each  acbssion  of  heat.  The 
fluid  tar  from  the  humus,  the  slightly  viscous  tar  from  the  re- 
sinoid  bodies,  and  the  rich  heavy  tar  from  the  hydrocarbon  gases 
go  forward  as  vapors  with  the  advancing  gases  away  from  the  heat 
and  towards  cool  places.  It  must  be  evident  then,  that  as  the  heat 
spreads  to  the  zone  in  which  the  water  has  condensed,  that  this 
water  again  evaporates  and  renders  a large  amount  of  latent  heat, 
so  cooling  it  down  and  leading  to  the  condensation  of  the  tar 
vapors.  When  in  turn  this  is  reached  by  the  advancing  temperature 
and  is  heated  to  350°  or  400°G.  , it  is  only  the  more  volatile 
portions  that  distil  and  a deposit  of  pitch  is  left,  which  binds 
the  half  formed  coke.  As  the  temperature  rises  still  higher,  the 


• ■ 


. 

. 


• 

- ’.V  ■ 

• 

. 

• 

. 


(7) 

residues  and  the  tar  still  further  decompose  until  the  hard  coke  is 
left.  That  tar,  which  is  least  volatile  and  leaves  the  largest 
amount  of  pitch,  is  the  most  valuable  as  far  as  coking  is  concerned. 
If  all  distillation  of  the  tar  out  of  the  coal  could  be  prevented, 
then  we  cpuld  coke  our  so-called  non-coking  coalG. 

Dr.  HargerlO  states  that  it  is  generally  held  that  the  coking 
property  of  coal  is  due  to  the  presence  of  resinic  material.  In 
addition  to  this  the  better  coking  coals  have  a class  of  bodies 
( which  have  a definite  melting  point  and  are  not  affected  by  air 
or  by  heating)  in  sufficient  quantity  to  renddr  the  whoiLe  mass 
liquid  and  so  will  form  good  coke.  Anderson,  Roberts,  and  Prof. 

Lewes  considered  these  as  hydrocarbons  bodies  and  in  strongly 
coking  coal  it  is  the  presence  of  such  bodies  which  cauee  coking 
even  though  the  resins  are  oxidized  or  saponified.  The  assumption 
of  such  bodies,  according  to  Dr.  Harger,  is  entirely  unjustifiable 
in  the  absence  of  data  to  prove  their  existence. 

Parr  and  Oli^1-'-  in  the  resume  of  their  work  developed  certain 
facts.  First,  the  formation  of  coke  depends  on  the  presence  of 
certain  constituents  having  a melting  point  which  is  lower  tha h the 
temperature  at  which  the  decomposition  or  carbonization  takes  place. 
Second*,  these  constituents  can  be  readily  oxidized  and  when  oxidized 
their  coking  properties  are  sadly  impaired.  Third,  coals  containing 
an  excessive  quantity  of  the  coking  substance  produce  a light 
porous  coke.  Fourth, by  the  use  of  temperatures  between  400°C.  and 
500°C. , all  of  the  resulting  products  are  of  a type  distinctly 
different  from  those  obtained  by  the  usual  high  temperature  pro- 
cedure. 


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(8) 

Bonel2  mentions  the  work  of  Dr.  Smythe,  who,  in  1851,  worked 
with  different  solvents  for  coal.  He  employed  benzene,  chloroform, 
ethyl  alcohol,  ethyl  ether,  light  petroleum,  and  acetone.  He  pre- 
cipitated the  resins  from  the  solutions  with  petroleum  ether. 
Benzene,  the  most  efficient  solvent,  extraxted  about  three  per  cent 
of  the  coal. 

Prof.  Bedson'"-'  in  1899  used  pyridine  in-; a Soxhlet  extractor 
as  a solvent  for  coal.  His  results  show  that  there  is  practically 
no  correlation  between  the  amounts  of  pyridine  extraction  and 
either  their  gas-making  qualities  or  their  yield  of  volatiles.  The 
extracts  were  rich  in  volatile  constituents  and  in  an  assay  test 
gave  a sort  of  coke,  whereas  the  residues  from  the  treatment  gave 

no  indication  of  any  coking  property  whatsoever. 

14- 

Dr.  Karger  used  sealed  tubes  for  extraction  work  and  noticed 
greater  action.  Prom  the  fact  that  ultimate  analyses  of  the  por- 
tions of  the  coal,  after  an  extraction  with  pyridine,  show  a larger 
per  cent  of  nitrogen  than  the  pure  coal,  he  claimed  that  the  action 
of  pyridine  must  be  other  than  that  of  a pure  solvent. 

P.F.Reinsch1'  did  some  work  in  1885  and  at  that  time  concluded 
that  by  means  of  solvents  we  could  isolate  from  coals  two  different 
kinds  of  substances,  distinguishable  by  their  behavior  toward  al- 
kaline solutions  and  the  subsequent  behavior  of  the  extract  with 
mineral  acids.  Wahl^  worked  with  some  coals  from  Spain,  using  py- 
ridine as  a solvent,  and  secured  from  six  to  twenty  six  per  cent 
extractions,  while  the  coal  would  lose  from  five  to  six  per  cent 

Ip 

of  volatile  matter.  Lewes"'  gives  as  a conclusion  to  his  work  with 
pyridine  and  his  treatment  of  the  residues  and  extracts  with  sodium 


(9) 

hydroxide  the  following:  That  the  resin  constituents  condition  the 

coking  of  the  coal  and  that  they  are  of  two  kinds.  The  one  is  easilj 

oxidized  and  saponified  with  alkali  and  it  is  soluble.  The  other  ie 

not  easily  oxidized,  is  non- saponifiable,  end  forms  a compound  with 

pyridine.  This  latter  class  he  thinks  may  be  the  hydrocarbons  from 

decomposed  resins  to  which  Or.  Harger  , as  stated  above,  took  such 

18 

exception.  Frazer  and  Hoffman  did  a great  deal  of  work  on  the 
constituents  of  coal  that  are  soluble  in  phenol.  They  treated  ex- 
tracts with  sodium  hydroxide  and  then  with  organic  solvents,  such 
as  ether  and  alcohol,  and  suceeded  in  dividing  the  coal  ,into 
various  portions.  No  definite  or  absolutely  accurate  information 
was  given. 

19 

Parr  and  Hadley  ' worked  with  phenol  as  a solvent  and  give  as 
a result  of  such  work  the  following;  (l)  The  extract  is  the  vital 
constituent  concerned  in  the  coking  of  coal.  (2)  It  conforms  to  the 
principle  found  before  of  having  a definite  melting  point, \yhich  is 
lower  than  that  of  decomposition.  (3)  The  cellulosic  (residue)  has 
the  greatest  avidity  for  oxygen.  They  found  that  neither  the  extract 
or  the  residue  gave  real  coke,  but  when  mixed  in  the  original  pro- 
portions they  would  coke. 

20 

Cherry  working  on  the  effect  of  oxygen  on  coal  came  to  the 
conclusions:  (l)  That  in  oxidation  the  first  constituent  to  be 
affected  is  the  cellulosic  portion.  (2)  That  oxidation  of  the  c 
cellulosic  portion  alone  is  sufficient  to  destr'V  the  coking  pro- 
perties of  the  coal.  (3)  That  a reaction  occurs  at  the  fusion  tem- 
perature between  the  oxidized  cellulosic  portion  and  the  resinic 
portion,  whereby  the  resinic  material  is  so  altered  that  it  cannot 


lute  the  mass. 


.... 


. 


. 


. 


: 

< 

. 

. 

. 

, 


(10) 

Pi 

W.  A.  Bone  reports  that  the  absorption  by  coal  of  oxygen  is 
slight  at  ordinary  temperatures  but  that  nearer  100°C.  it  increases 
and  is  attended  by  the  formation  of  two  oxides  of  carbon  and  steam. 
These  products  result  from  the  decomposition  of  some  unstable  body 
previously  formed  by  the  absorption  of  oxygen.  Fischer  and  Groppel 
found  that  low  yields  in  extraction  could  be  increased  by  pre- 
heating the  coal  for  a short  time.  By  heating,  the  structure  of  the 
coal  is  broken  down  so  that  the  tar  forming  products  can  be  com- 
pletely extracted.  The  temperature  necessary  for  this  action  wa# 
found  to  be  from  550°C.  to  600~C.,  followed  by  a papid  cooling. 
Fischer  and  Gludd^  tried  the  extraction  of  coal  with  liquid  SO-, 
and  found  that  it  destroys  the  binding  power  and  leaves  the  coal  as 
a fine  powder.  By  use  of  ozone  they  they  converted  the  coal  into  a 

ninety  two  per  cent  soluble  substance; 

24 

Hobart  in  his  studies  of  the  effect  of  oxygen  and  carbon  di- 
oxide on  coal,  noticed  that  the  coking  power  of  the  coal  was  des- 
troyed by  the  oxygen,  but  could  not  find  any  effect  by  the  carbon 
dioxide.  He  comes  to  the  conclusion  thatare  several  compounds  in 
coal,  each  with  a definite  melting  point.  If  these  compounds  are 
oxidized,  then  either  (l)the  melting  point  is  raised  due  to  the 
formation  of  higher  molecular  weight  compounds  so  that  the  decom- 
position point  occurs  before  the  melting  point  or  (2)  the  oxidation 
decomposes  and  breaks  up  the  coal  into  unstable  substances  of  in- 
definite melting  point.  He  thinks  that  the  cellulosic  constituent 
takes  the  oxygen  in  the  first  place  and  gives  it  to  the  resinic 
parts  when  the  temperature,  favorable  for  this  reaction  occurs. 


. 

. 

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. 

. 

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. 

. 


0 


, 


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(11) 

II.  EXPERIMENTAL 

A Franklin  county  coal  was  chose#; for  use  in  the  investigation 
One  portion  was  taken r£o  he  used  as  the  sample  of  fresh  coal  and 
another  portion  was  artificially  weathered  and  used  as  the  sample 
of  oxidized  coal.  W. A. Bone  and  F.  Hohart,  working  independently, 
noticed  that  oxidation  ot  the  absorption  of  oxygen  by  coal  would  pF 
progress  readily  if  carried  out  at  a temperature  of  100°C.  There- 
fore the  sample  to  ,be  oxidized  was  placed  in  a bottle,  which  was 
supplied  with  oxygen  under  a slight  pressure,  and  kept  in  an  oven 
at  a temperature  of  110°C.  for  several  weeks. 

The  method  of  extraction  to  be  used  was  then  determined  upon* 
Several  ideas  wrere  tried  out,  including  that  of  using  a Soxhlet  ex- 
tractor with  a regular  as  well  as  an  alundura  thimble.  The  use  of  a 
large  Erlenmeyer  flask  connected  to  a reflux  condenser  with  the 
coal  and  solvent  in  the  flask  and  heated  in  an  electric  furnace  to 
a temperature  of  258°C.  proved  to  be  the  simplest,  roost  rapid,  and 
efficient  procedure.  It  was  therefore  adopted  as  the  method  to  be 
used  forthwith.  Fifty  grams  of  coal  and  three  hundred  cc.  of  sol- 
vent were  taken  for  each  run.  A mixture  of  litharge  and  glycerine  w 
was  used  to  seal  the  apparatus.  A rubber  tube  connected  the  top  end 
of  the  reflux  condenser  to  a pair  of  bottles  containing  alkaline 
pyrogallol,  and  this  was  so  arranged  that  no  air  could  enter  the 
apparatus  without  passing  thru  the  solution  and  thus  being  freed  of 
oxygen.  The  action  was  permitted  to  continue  for  twenty  four  hours 
in  each  case.  The  solution  was  then  filtered  end  the  residue  re- 
turned to  the  flask  for  another  extraction  under  the  same  condition* 
This  was  repeated  three  times  for  each  sample  taken. 


(12) 

The  accumulated  extracts  from  the  three  runs  on  each  sample 
were  then  distilled  to  a small  volume  in  an  ordinary  distilling 
flask,  transferred  to  a large-sized  side-arm  test  tube  and  taken 
to  drynessin  an  atmosphere  of  nitrogen  at  a temperature  of  260°C. 
The  residues  were  then  washed  repeatedly  with  alcohol  and  ether.  •- 
The  washings  were  at  first  handled  separately  from  the  main  ex- 
tracts hut  later  were  all  combined  and  taken  to  dryness  as  one.  The 
residues  were  dried  in  an  oven  with  an  atmosphere  of  nitrogen  at  a 
temperature  of  110°C. 

The  proximate  and  ultimate  analyses  of  the  coals,  residues, 
and  extracts  were  made  using  standard  methods  of  analyses.  The 
heat  of  combustion  was  determined  in  a Parr  Adiabatic  Oxygen  Bomb 
Calorimeter,  the  total  carbon  in  a Parr  To&&l  Carbon  Apparatus, 
and  the  nitrogen  by  the  Keldjahl- Gunning  method  using  a .098  N 
acid  and  a .104  N KOH  solution.  The  hydrogen  and  the  Oxygen  were 
determined  by  calculation  from  DuLongs  formulae.  The  sulphur  was 
determined  by  the  fusion  of  the  sample  and  the  subsequent  pre- 
cipitation of  the  sulphur  as  BaSO^. 

The  carbonization  experiments  were  carried  out  on  ten  gram 
samples.  The  retort  was  made  by  sealing  one  end  of  a pyrex  tube, 
one  inch  in  diameter  and  ten  inches  long,  and  attaching  a side  arm 
to  it  very  near  the  top.  This  was  connected  to  a tar  and  water 
receptacle,  which  in  turn  led  to  a CaCl2  U-tube,  which  would  re- 
move the  last  traces  of  moisture  from  the  passing  gases.  This  led 
to  a KOH  bulb,  in  which  inp  place  of  KOH  was  a solution  of  CdS04 
acid  in  H2SO4.  This  would  remove  the  H2S  and  the  NH3 . The  final 
peice  in  the  train  was  the  aspirator  bottle  to  collect  the  gases. 


Z7/  0-  <J  /f  /S 


<*)  n-t-,  J >3.^ 


' 


' 


' 


(13) 


Thru  the  cork  at  the  top  end  of  the  retort  a small  tube,  sealed  at 
one  end  , was  inserted.  This  extended  to  the  bottom  and  the  ma- 
terial to  be  carbonized  was  placed  around  it.  One  of  the  thermo- 
couples waB  placed  in  this  tube  and  accurate  measurements  of  the 
temperature  could  be  secured  at  any  time  during  therun.  A very 
small  metallic  tube  was  also  put  thru  the  cork,  thru  which  nitro- 
gen was  passed  to  sweep  out  the  system  when  it  was  desired.  The 
thermocouples  were  standardized  against  Zn  and  Al,  using  a Weston 
millivoltmeter  as  a recorder  of  the  induced  current. 

Increases  in  the  weight  of  the  tar  and  water  receptacle  and 
the  CaCl0  tube  during  a carbonization  gave  the  weight  of  tar  and 
the  total  water.  By  subtracting  from  this  weight  the  amount  of 
water  of  hydration,  which  was  calculated  from  theoven  drying  loss 
and  the  amount  of  coal  taken,  the  weight  of  the  tar  and  the  water 
of  decomposition  was  secured.  The  increase  in  the  weight  of  the 
CdS©4  bulb  gave  thw  weight  of  the  H2S  and  the  The  apparatus 

was  swept  with  nitrogen  before  starting  and,  v/hen  the  desired  tem- 
perature had  been  reached,  it  was  again  sewpt  inorder  to  .carry 
away  all  the  gases  evolved.  Nitoogen  was  passed  thru  concentrated 
sulphuric  acid  to  remove  moisture  since  it  was  stored  above  water. 
Gases  were  analyzed  in  a modified  D’Orsatt  apparatus. 

A solution  of  ten  per  cent  KOH  in  absolute  alcohol  was  tried 
as  a solvent.  The  method  above  was  used  except  that  a greater  pro- 
portion of  solvent  to  coal  was  taken,  a temperature  of  80  'C.  was 
used,  and  the  reflux  condenser  was  water  cooled. 


. 


• 

, 

. 

, 

. 

. 

< 

■ 

1 

. 

' 

. 

< 

■ 

* 

. 

« 

' 

• < 

. 


< 


III.  RESULTS 

The  fresh  and  the  oxidized  coal  had  an  equal  and  constant 
quantity  of  material  removed  by  the  di-phenvl  ether  during  three 
repeated  extractions.  Three  percent  wqs  removed  in  the  first  ex- 
traction, seventy  five  hundredths  per  cent  in  the  second,  and  three 
tenths  per  cent  in  the  third.  This  totaled  approximately  four  per 
cent  for  the  three  operations. 

An  extraction  of  the  coal  with  a solution  of  ten  per  cent  KOH 
in  absolute  alcohol  was  also  tried  and  it  was  found  that  four  and 
one  half  per  cent  of  the  coal  was  removed.  This  extract  after  being 
dried  and  weighed  was  tree.ted  with  di-phenyl  ether,  which  removed 
sixteen  and  eight  tenths  per  cent.  The  original  extract  gave  in  a 
crucible  test  a coke  structure,  whereas  after  th§  action  Of  the  di- 
phenyl ether  it  would  not  take  on  the  coke  structure  whatsoever. 


Table  I. 

Proximate  analyses  of  products. 
Moisture  free  basis. 


1 

Fresh 

Coal 

% 

Oxid. 

Coal 

* 

Res. 

Fresh 

Coal 

% 

Res. 

Oxid. 

Coal 

% 

Ext . 

Fresh 

Coal 

% 

Ext . 
Oxid. 
C oal 

% 

V.  Matter 

26.39 

33.16 

37.23 

38.25 

52.84 

62.40 

F.  Carbon 

55.75 

58.97 

54.47 

53.40 

46.28 

36.65 

Ash 

7.84 

7.87 

8.30 

8.35 

.88 

.95 

Sulfur 

1.36 

1-33 

1.00 

1.09 

.40 

.40 

Unit  B.T.U. 

14588 

13,580 

14,550 

13.530 

15,190 

15,210 

Pyritic  Sulfur 

• 59 

• 58 

.32 

.29 

.00  .00 

— 1 — r r. 

Quality  of  coke 

good 

powder 

bad 

powder 

semblance  same 

I 


t 


< 


t 


n (15) 

Table  II. 

Ultimate  analyses  of  fresh  coal  and  its  products. 
Moisture  free  basis.  Results  also  in  % coal. 

Residue. 
Dry  ^Coal 

Extract . 

Dry  ^Coal 

Total 

of 

7° 

■ y 

Coal 

% 

r 

Yield 

96.00 

4.00 

100.00 

Ash 

8.30 

7.97 

.88 

.03 

8.00 

7.34 

Sulfur 

1.00 

.96 

.40 

.01 

.97 

1.36 

Nitrogen 

1.53 

1.47 

1.58 

.06 

1.53 

1.63 

T.  Carbon 

73.45 

70.45 

83.47 

3*34 

73.79 

72.30 

Hydrogen 

507 

5.15 

5.51 

.22 

5.37 

5*  64 

Oxygen 

10.35 

9.95 

8.16 

.32 

10.27 

10.72 

B.T.U. 

13.205 

12,670 

14,998 

600 

13,270 

13,314 

Ultimat 

Moi 

e analys 
sture  fr 

Ta' 

es  of  Ox 
■ee  basis 

bl|- III. 

idized  coal  and  its  products. 
Results  also  in  % coal. 

Residue 
Dry  ^Coal 

Extract 
Dry  $Coal 

Total 

% 

Coal 

% 

Yield 

96.00 

4.00 

100. 00 

Ash 

8.35 

8.00 

.95 

.03 

8.03 

7.87 

Sulfur 

1.09 

1.04 

.40 

.01 

1.05 

1-33 

Nitrogen 

1.  51 

1.44 

1.56 

.06 

1. 50 

1.64 

T.  Carbon 

70.89 

68.30 

84.35 

3-48 

71.78 

70.43 

Hydrogen 

4.80 

4.51 

5.38 

. 20 

4.71 

5.12 

Oxygen 

13.36 

12.68 

7.36 

.29 

12.97 

13.61 

B.T.U. 

12. 260 

11,710 

15,039 

600 

12,310 

12,487 

(16) 

Table IV. 

Results  of  heating  the  coals  and 

' 

their  products  to  600°C. 

\ 

Fresh 

Coal 

Oxid. 

Coal 

Res. 

Fresh 

Coal 

Res. 

Oxid. 

Coal 

Ext. 

Fresh 

Coal 

Ext  • 
Oxid. 
Co  al 

Wt.  (dry)  gms. 

9.6 

9.83 

9.64 

9.89 

10.00  ' 

10.00 

Time  of  test  min. 

90 

90 

90 

90 

90 

9° 

Coke  %. 

7.15 

7.42 

6.  64 

6.79 

5.80 

5.10 

Tar  & Hp$  decomp.  % 

1.55 

1.22 

2.07 

1.96 

4.30 

3.90 

H2S  & NH3  % 

.04 

.04 

.03 

.03 

.02 

.00 

*Gas  cc.  per  10  gms. 

885 

1000 

800 

1200 

1300 

1250 

CM 

0 

0 

63 

141 

47 

158 

46 

87 

246 

°2 

41 

39 

77 

62 

264 

c2h4  " 

29 

21 

14 

12 

31 

52 

c6h6 

6 

2 

19 

3 

4 

10 

H2 

218 

268 

187 

308 

135 

180 

CO  " 

42 

79 

41 

213 

22 

21 

CH|  " 

410 

449 

364 

430 

780 

465 

c2h6 

76 

** 

49 

** 

V-  y. 

7VT 

181 

Factor  n 

1.162 

** 

1.12 

** 

** 

1.27 

Composition  of  gas 

C0?  % 

7.2 

14.1 

5.9 

13.  2 

3.5 

7.0 

o3  % 

4.7 

3.9 

9.6 

5.2 

■ 

20.5 

19. 71 

c2h4  % 

3.3 

2.1 

1.8 

1.0 

2.4 

4.2 

c6h6  % 

.7 

.2 

2.4 

•3 

•3 

• 9 

CM 

w 

24.7 

26.8 

23*5 

25.7 

10.4 

14.4 

CO  % 

4.3 

7.9 

5.1 

17.8 

1.7 

1.7 

ch4  % 

46. 6 

44*9 

45 . 6 

43.0 

60. 8 

37.2 

CpHA  % 

8.  6 

** 

6.1 

** 

1 

**  - 14,5- 

— ^4 

Figured  to  yiei 

& logins. 

dry  ana 

n2  free 

•i 


i 


c,r‘ 


» 


1 

KOH 

Extract 

KOH 

Residue 

— ^ 

Residue 

after  di-phenyl 
ether  extraction 

Ash 

2.76 

14. 36  

V.  Matter 

52.96 

48.20 

39.92 

Coking 

coke  structure 


no  coke 

no  coke 

U6a) 

Table  V. 

Analyses  of  products  from  alcoholic  KOH  extractions. 


(17) 

IV.  DISCUSSION  OF  RESULTS. 

Decided  differences  in  fresh  and  oxidized  coal  are  apparent 
from  a study  of  the  results  and  these  are  in  accord  with  the  find- 
ings of  former  investigations.  The  calorific  value  is  less  in  the 
oxidized  coal.  This  can  he  explained  on  the  ground  that  the  oxid- 
ation is  in  effect  a partial  combustion  and  the  noted  decrease  in 
heating  value  is  generated  in  the  C04I  during  the  oxidizing  period. 
It  is  also  seen  that  the  weathered  coal  will  not  coke. 

The  amount  of  extraction  is  the  same  for  the  fresh  and  the 
oxidized  coal.  The  amount  extracted  from  the  coal  is  not  large  and 
consequently  differences  in  the  solubilities  of  the  two  coals,  if 
present,  would  not  be  noticed.  In  Table  I,  differences  between  the 
coals  and  the  products  of  the  coals  can  be  noticed.  The  ash  seems 
to  have  been  unaffected  by  the  solvent,  and  there  are  no  indications 
of  any  other  reagent  activity  having  occured,  so  the  di-phenyl  ether 
must  be  a true  solvent.  The  residues  have  lees  heating  value  than 
their  respective  coals.  THis  follows  from  the  fact  that  part  of  the 
pure  coal  substance  has  been  removed.  It  is  likewise  noted  that  in 
heating  value,  the  residue  of  the  oxidized  coal  differs  from  the 
residue  of  the  fresh  coal  by  the  same  amount  that  the  oxidized  coal 
differs  from  the  fresh  coal,  whereas  the  extracts  from  the  two  are 
alike.  This  confirms  the  theory  that  the  oxygen  affects  the  cell- 
ulosic  constituent  first  and  that  if  it  does  affect  the  resinic  it 
must  do  so  at  a higher  temperature.  Cherry2{l  and  Hobart advocate 
this  idea. 

Di -phenyl  ether  affects  the  coking  constituent  of  the  coal  for  1 
the  fresh  coal  does  not  coke  after  wi  extraction  with  this  solvent, 


. 

■ ■ 

. 


. 

* 

- 

. 

c 

1 

« 


< 

. 


. 


. 

. 


, 

. 

. 

. 


(18) 

The  Extracts  from  both  coals  coke.  Again  the  resinic  part  seems  to 
show  that  it  is  unaffected  hy  the  oxygen.  In  Tables  II  and  III  the 
per  cent  of  oxygen  is  eeen  to  he  higher  in  the  weathered  coal  than 
in  the  fresh  coal.  This  same  fact  is  true  for  the  residues  of  the 
coals,  hut  is  not  true  for  the  extracts.  The  oxygen  must  he  con- 
nected with  the  cellulosic  portion.  According  to  White,  the  extract 
can  he  of  higher  oxygen  content  than  of  hydrogen.  The  analysis  o-f 
the  extract  points  to  tjxe  same  fact.  That  weathering  does  not  affect 
the  extract  is  attested  hy  the  fact  the  extract  from  the  weathered 
coal  does  not  show  higher  oxygen  than  that  from  the  fresh  coal. 

Q 

Lewes'  argued  that,  if  it  was  the  cellulosic  part  that  had  the 
greater  oxygen  and  the  lower  hydrogen,  then  hy  coking  ata  low  tem- 
perature and  thud  removing  the  resinic,  the  coke  should  analyze 
still  higher  in  oxygen  and  lower  in  hydrogen.  This  same  principle 
would  he  applied  if  the  resinic  were  removed  hy  extraction.  He 
found  that  the  resulting  product  was  lower  in  hydrogen  hut  also 
lower  in  oxygen.  The  analysis,  when  the  resinic  was  removed  hy 
solvent,  shows  the  same  to  he  true  hut  though  lower  in  oxygen  in 
absolute  amount,  it  is  higher  proportionately. 

Turning  to  the  carbonization  data,  it  is  noticed  that  the 
oxidized  coal  shows  a large  increase  in  the  per  cent  of  CO9,  app- 
roximately the  same  amount  of  hydrogen,  and  a decrease  of  paraffin 
hydrocarbons.  This  is  in  conformance  with  the  theory  as  originally 
set  forth  at  the  start  of  this  work.  The  fact  presents  itself  that 
large  differences  in  properties  occur  in  the  residues  rather  than 
in  the  extracts.  It  is  seen  that  a larger  percentage  of  C02  is 
present  in  the  oxidized  residue  than  in  that  of  the  fresh,  about 
the  same  per  cent  of  hydrogen,  and  also  the  same  per  cent  of  par- 


•• 


. 

. 

. 

< 

• 

■ • 

. 

. 


, 


< ••  ' * 

-X 

. 

* 

< 


, 


. 


. 


( 

t 


. 


(19) 


affins.  The  extracts  show  almost  the  same  percentages  of  each  of 
these  constituents.  Forter  and  Taylor?  argued  that  the  resinic  part 
decomposes  largely  to  give  the  paraffin  hydrocarbons  and  that  it 
may  give  some  hydrogen  as  a direct  decomposition  product.  The  ex- 
tracts do  show  tfery  much  larger  percentages  of  the  paraffin  hy- 
drocarbons than  their  coresponding  residues  and  they  do  ha foe  a 
fairly  large  hydrogen  content.  Wheeler0  claimed  that  the  resinic 
would  not  give  hydrogen  as  a decomposition  product.  We  note  also 
that  Wheeler,  Porter,  and  Taylor  agree  that  the  carbon  monoxide 
comes  from  the  cellulosic  portion.  The  data  shows  that  though  it 
is  not  great  in  either  case  that  it  is  greater  by  far  in  the  gas 
from  the  residues  than  in  the  gas  from  the  extracts.  The  coke  de- 
rived from  the*tar  in  the  carbonizat ion  test  was  very  much  like  a 

g 

pitch  coke  and  so  the  pitch  structure  idea  of  Lewes  fOr  coking 
has  some  basis. 

It  is  also  to  be  noted  that  in  the  distillation  of  the  residues 
tar  is  still  secured.  This  would  indicate  that  the  resinic  material 
has  not  been  all  removed  and  if  this  is  so,  then  the  differences 
already  so  pronounced  between  the  residues  and  extracts,  would  be 
greatly  increased  if  the  extraction  were  complete. 

The  alcoholic  potash  extract  of  the  coal  coked.  After  this 
extract  had  been  acted  upon  by  di-phenyl  ether  it  did  not  coke.  This 
indicates  that  the  KOH  solution  removes  at  least  some  of  the  coking 
constituent  and  also  some  other  material.  This  added  material  is  no 
all  mineral  for  the  ash  content  of  the  extract  is  low. 


:l 


5 


* extract. 


, 


- 


' 

. 


. 


. 


■ . 


(20) 

V.  CONCLUSION. 

1.  Di-phenyl  ether  removes  a part  at  least  of  the  coking  con- 
stituent of  coal. 

2.  Di-phenyl  ether  is  "better  in  some  respects  as  a solvent  than 
phenol  or  pyridine.  It  is  easier  to  work  with  an ci  to  wash  from  the 
residue  than  is  phenol.  It  does  not  form  addition  products  with  the 
coal  substance  as  does  pyridine.  It  does  not  extract  a great  deal 

of  the  coal  and  so  its  usefulness  as  a solvent  is  limited  in  this 
respect . 

3.  Oxidation  destroys  the  coking  property  of  the  coal. 

4.  Oxidation  decreases  the  heat  of  combustion  of  the  coal. 

5.  Oxidation  affects  the  cellulosic  constituent  and  the  effect 
of  oxidation  is  therefore  best  noticed  thru  a study  of  the  residue. 

6.  Differences  between  the  fresh  and  the  oxidized  coal  in  both 
ultimate  andlysdbs  and  carbonization  work,  occur  similaarly  in  the 
residues  from  the  fresh  and  the  oxidized  coal.  The  extracts  from  the 
two  are  fundamentally  alike. 

7.  The  use  of  a double  extraction  with  di-phenyl  ether  and  a 
solution  of  10%  KOH  in  absolute  alcohol  does  not  indicate  that  it 
will  give  a great  deal  of  information  regarding  the  constitution  of 

coal. 


♦ 


- 


. 

. 

* 

. 

• 

< 

• 

. 

. 


' 


(21) 

VI.  BIBLIOGRAPHY. 

1.  White  and  Thiessen,  Bull.  38,  Bureau  of  Mines. 

2.  Cross  and  Eevan,  Phil.  Mag.  352,1882 
(abstracted  in  Bull  No.  24,  U.I.  Exp.  Sta.  page  4.) 

3.  Anderson  and  Roberts,  Jour.  Soc.  Chen.  Ind. , 1013,  1918. 


4. 

Parr  and  Francis,  Bull.  No. 
(The  modification  of  Illinoi 

24,  U. 
s coal 

I . Exp . 
by  low 

. Sta. 

temperature 

he at ing) 

c 

, • 

David  White  , Bull. 

No.  29, 

Bureau 

of  Mines,  1911. 

6. 

Burgess  and  Wheeler, 

Jour.  Chem  Soc 

. V9 7, 

page  1917, 

year  1910 

h (i  11 

11 

11  11 

V99, 

" 649 

” 1911 

tt  11  11 

it 

11  11 

V105 

" 131 

" 1914 

Clark  and  Wheeler 

ti 

11  11 

V103 

" 1705 

” 1913 

7.  Porter  and  Taylor,  Tech.  Paper  No.  140,  Bureau  of  Mines,  1916. 

8.  Lewes,  text  ’ The  Carbonization  of  Coal*  1914. 

9.  White,  U.S.  Geol  Paper  85®,  pp  65-83- 

11C.  Dr.  Harger,  Gas  World  V60,  page  195 » 1914. 

11.  Parr  and  Olin,  Bull.  No.  79,  U.I.  Eng.  Exp.  Sta.,  1915* 

12.  W.A.  Bone,  text  ’ Coal  and  Its  Scientific  Uses’. 

13.  Prof.  Bedson,  J.S.C.I.  V27,  147,  1908. 

14.  Dr.  Harger,  J.S.C.I.,  page  389,  year  1914. 

15.  P.F.Reinsch,  J.C.S.,  No. 48,  page  876,  year  1885* 

16.  Wahl,  Compt.  Rendu,  No.  154,  page  1094,  year  1912. 

17-  Lewes,  Progressive  Age,  No  29,  page  1030 , year  1911. 

18.  Erazer  and  Hoffman,  Tech.  Paper  No.  5,  Bureau  of  Mines,  1912. 

19.  Parr  and  Hadley,  Bull.  no.  76. , Eng.  Exp.  Sta. , 1914. 

20.  Cherry,  Theses  for  B.S.  Degree,  Uof  I.  L92C 

21.  W.A.  Bone,  text  ’Coal  and  Its  Scientific  Uses’. 

22.  Fischer  and  Groppel,  J.S.C.I.,  No.  38,  400a,  1919* 


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